CN102875520B - Synthetic method of fluoro carbonic ester - Google Patents
Synthetic method of fluoro carbonic ester Download PDFInfo
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- CN102875520B CN102875520B CN201210361558.3A CN201210361558A CN102875520B CN 102875520 B CN102875520 B CN 102875520B CN 201210361558 A CN201210361558 A CN 201210361558A CN 102875520 B CN102875520 B CN 102875520B
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Abstract
The invention provides a synthetic method of fluoro carbonic ester. The synthetic method is characterized in that potassium fluoride serves as a fluorinating agent for fluorinating chloro carbonic ester under the effect of a phase transfer catalyst in an organic solvent, so as to synthesize fluoro carbonic ester; the molar quantity of phase transfer catalyst is 0.1 to 10% that of chloro raw material; and synthetic reaction is carried out at a temperature of 50 to 200 DEG C; and phase transfer catalyst is cucurbituril and derivate thereof.
Description
Technical field
The present invention relates to phase-transfer Wittig reaction technical field, is a kind of synthetic method of fluoro carbonic ester, is specifically related to the synthetic method of a kind of fluoro carbonic ester of phase-transfer catalysis.
Background technology
Fluorinated organic compound has excellent performance because of it and extraordinary effect obtains extensive accreditation in actual applications.Relate to the important industry of many national economy such as national defence, military project, aerospace, medicine, automobile, petrochemical industry.Fluoro carbonic ester is the important fluorinated organic compound developed in recent years, and it all has broad application prospects in medical material field and field of lithium ion battery.The synthesis of fluoro carbonic ester is raw material mainly through chlorinated carbonates, with metal fluoride salt for fluorination reagent, carries out halogen exchange reaction and obtains.But because metal fluoride salt solubleness in organic phase is very little, cause this inhomogeneous reaction very difficult, often condition is harsher and productive rate is very low.
In order to increase the solubleness of metal fluoride salt in organic phase, improve the speed that fluorion participates in reaction, introducing phase-transfer catalyst becomes the optimal path addressed this problem.
Patent CN101870687 proposes with 18-hat-6 ethers for fluorinated ethylene carbonate prepared by phase-transfer catalyst, and the selectivity of fluorinated ethylene carbonate only has 78.5%.Patent CN101210005 reports with polyoxyethylene glycol as phase-transfer catalyst, and the yield of final FEC only has 55.4%.
Though there is the report of a few class phase-transfer catalyst at present, productive rate is lower, and effect is not very good.
Summary of the invention
The present invention is that disclosing a kind of take Cucurbituril as the method for phase-transfer catalyst synthesizing fluoro carbonic ether.The method is raw material with chlorinated carbonates, is fluorination reagent, is catalyzer, prepares fluoro carbonic ester in organic solvent by halogen exchange reaction with Cucurbituril with Potassium monofluoride.
Cucurbituril is the novel cavity macrocylc compound of a class, and it is formed by the condensation under the catalysis of acid of glycosides urea groups, and the element number difference according to polymerization is divided into Cucurbituril [5] ~ Cucurbituril [10] not.Cucurbituril is the macrocylc compound of picture drum type, and its port is multiple carbonyl composition, has very strong clathration to metallic cation.Therefore, when interacting with metal pentafluoride salt, Cucurbituril can make the exposed degree of fluorion increase to the Inclusion property of metallic cation, because this enhancing the ability of fluorion attack halohydrocarbon, considerably increases the activity of reaction.
Chlorinated carbonates as above has following constitutional features:
Wherein R is the alkyl of H or C1 ~ C12 or the alkoxyl group of C1 ~ C4.
The fluoro carbonic ester of synthesis described above has following constitutional features:
Wherein R is the alkyl of H or C1 ~ C12 or the alkoxyl group of C1 ~ C4.
The present invention is a kind of synthetic method of fluoro carbonic ester; It is characterized in that:
In organic solvent by the effect of phase-transfer catalyst, as fluorizating agent, fluoridation is carried out to chlorinated carbonates with Potassium monofluoride, synthesizing fluoro carbonic ether; The consumption of phase-transfer catalyst is 0.1% ~ 10% of the amount mole number of chloro raw material; Synthesis reaction temperature is 50 ~ 200 DEG C of scopes;
Described phase-transfer catalyst is Cucurbituril and derivative thereof; Be selected from as Cucurbituril [5], Cucurbituril [6], Cucurbituril [7], Cucurbituril [8], Cucurbituril [9], Cucurbituril [10]; Its structure is as follows:
wherein n is the integer of 5 ~ 10;
Cucurbituril derivative is hydroxy-cucurbituril and alkoxyl group Cucurbituril, has following structure, and wherein R is the saturated alkane base of C1 ~ C12:
wherein n is the integer of 5 ~ 10.
According to synthetic method of the present invention, it is characterized in that: the catalysis effectiveness of this phase-transfer catalyst in fluoridation is carried out in organic solvent, described organic solvent comprises DMF, dimethyl sulfoxide (DMSO), acetonitrile, tetrahydrofuran (THF), tetramethylene sulfone; The usage quantity of this phase-transfer catalyst in fluoridation is that the molal quantity of chloro raw material is preferably 0.2% ~ 9%.The synthesis reaction temperature of this phase-transfer catalyst in fluoridation is preferably 50 ~ 120 DEG C.
The introducing of this catalyzer can reduce temperature of reaction, Reaction time shorten, raising reaction yield compared to existing technology.
Embodiment
Embodiment 1: the preparation of fluorinated ethylene carbonate
Take 150g (1.224mol) chlorocarbonic acid vinyl acetate, and 300ml dimethyl sulfoxide (DMSO) (DMSO) is put in 1000ml tri-mouthfuls of round-bottomed flasks, stirred at ambient temperature is even.Add the Cucurbituril [7] of Potassium monofluoride 145g (2.5mol) and 2.99g drying.Be warming up to 50 DEG C of stirrings and be warming up to 70 DEG C gradually after one hour, react after 4 hours at this temperature, carry out solid-liquid separation to this mixed solution, collecting filtrate, is 118.9g through gas chromatographic analysis fluorinated ethylene carbonate content.Reaction yield is 91.6%.
Embodiment 2: the preparation of fluorinated ethylene carbonate
Take 150g (1.224mol) chlorocarbonic acid vinyl acetate, and 300ml acetonitrile is put in 1000ml tri-mouthfuls of round-bottomed flasks, stirred at ambient temperature is even.Add the hydroxy-cucurbituril [8] of Potassium monofluoride 104.6g (1.8mol) and 4.0g drying.Be warming up to 50 DEG C of stirrings and be warming up to 70 DEG C gradually after one hour, react after 4 hours at this temperature, carry out solid-liquid separation to this mixed solution, collecting filtrate, is 117.5g through gas chromatographic analysis fluorinated ethylene carbonate content.Reaction yield is 90.5%.
Embodiment 3: the preparation of difluoroethylene carbonate
Take the two chlorocarbonic acid vinyl acetate of 157g (1.0mol), and 500mlN, dinethylformamide (DMF) is put in 1000ml tri-mouthfuls of round-bottomed flasks, and stirred at ambient temperature is even.Add the oxyethyl group Cucurbituril [6] of Potassium monofluoride 232.5g (4.0mol) and 4.99g drying.Be warming up to 60 DEG C of stirrings and be warming up to 90 DEG C gradually after one hour, react after 5 hours at this temperature, reach 99.2% through gas chromatographic detection feed stock conversion.Carry out solid-liquid separation to this mixed solution, collect filtrate, obtaining difluoroethylene carbonate content through gas chromatographic analysis is 106.1g.Reaction yield is 85.5%.
The preparation of embodiment 4:4-(methyl fluoride)-DOX-diketone
Take 4-(chloromethyl)-DOX-diketone 136.5g (1.0mol), and 300ml solvent sulfolane is put in 1000ml tri-mouthfuls of round-bottomed flasks, stirred at ambient temperature is even.Add the butoxy Cucurbituril [8] of Potassium monofluoride 87.2g (1.5mol) and 4.5g drying.Be warming up to 30 DEG C of stirrings and be warming up to 70 DEG C gradually after 0.5 hour, react after 4.5 hours at this temperature, reach 99.1% through gas chromatographic detection feed stock conversion.Carry out solid-liquid separation to this mixed solution, obtaining 4-(methyl fluoride)-DOX-diketone content through gas chromatographic analysis is 103.3g.Reaction yield is 86.0%.
The preparation of contrast case study on implementation fluorinated ethylene carbonate
Take 150g (1.224mol) chlorocarbonic acid vinyl acetate, and 300ml dimethyl sulfoxide (DMSO) (DMSO) is put in 1000ml tri-mouthfuls of round-bottomed flasks, stirred at ambient temperature is even.Add Potassium monofluoride 145g (2.5mol) and 2.99g polyoxyethylene glycol.Be warming up to 50 DEG C of stirrings and be warming up to 70 DEG C gradually after one hour, reacting after 4 hours at this temperature, is 88.1% through gas chromatographic detection feed stock conversion.Carrying out solid-liquid separation to this mixed solution, is 94.5g through gas chromatographic analysis fluorinated ethylene carbonate content.Reaction yield is 72.5%.
Claims (2)
1. the synthetic method of a fluoro carbonic ester; It is characterized in that:
In organic solvent by the effect of phase-transfer catalyst, as fluorizating agent, fluoridation is carried out to chlorinated carbonates with Potassium monofluoride, synthesizing fluoro carbonic ether; The consumption of phase-transfer catalyst is 0.1% ~ 10% of the molal quantity of chloro raw material; Synthesis reaction temperature is 50 ~ 200 DEG C of scopes;
Described phase-transfer catalyst is Cucurbituril and derivative thereof; Be selected from as Cucurbituril [5], Cucurbituril [6], Cucurbituril [7], Cucurbituril [8], Cucurbituril [9], Cucurbituril [10]; Its structure is as follows:
wherein n is the integer of 5 ~ 10;
Cucurbituril derivative is hydroxy-cucurbituril and alkoxyl group Cucurbituril, has following structure, and wherein R is the saturated alkane base of C1 ~ C12:
, wherein n is the integer of 5 ~ 10.
2. according to synthetic method according to claim 1, it is characterized in that: the catalysis effectiveness of this phase-transfer catalyst in fluoridation is carried out in organic solvent, described organic solvent comprises DMF, dimethyl sulfoxide (DMSO), acetonitrile, tetrahydrofuran (THF), tetramethylene sulfone; The usage quantity of this phase-transfer catalyst in fluoridation is 0.2% ~ 9% of the molal quantity of chloro raw material; Synthesis reaction temperature in fluoridation is at 50 ~ 120 DEG C.
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| CN105481822A (en) * | 2015-12-14 | 2016-04-13 | 苏州华一新能源科技有限公司 | Method for preparing fluoroethylene carbonate |
| CN114085148A (en) * | 2020-08-06 | 2022-02-25 | 天津市职业大学 | Preparation method and application of monofluoroethyl ethyl carbonate |
| CN112777818B (en) * | 2020-12-13 | 2022-11-15 | 中海油天津化工研究设计院有限公司 | Composite membrane photoelectrocatalysis fluidized bed treatment device and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1896120A (en) * | 2006-06-29 | 2007-01-17 | 四川大学 | Preparation of polyarylphenyl resin by phase-transferring catalyst |
| CN101870687A (en) * | 2009-04-24 | 2010-10-27 | 中国科学院福建物质结构研究所 | Method for synthesizing fluoroethylene carbonate by phase-transfer catalysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896120A (en) * | 2006-06-29 | 2007-01-17 | 四川大学 | Preparation of polyarylphenyl resin by phase-transferring catalyst |
| CN101870687A (en) * | 2009-04-24 | 2010-10-27 | 中国科学院福建物质结构研究所 | Method for synthesizing fluoroethylene carbonate by phase-transfer catalysis |
Non-Patent Citations (1)
| Title |
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| 葫芦[6]脲衍生物的合成及其分子识别作用光谱法研究;葛小辉;《中国优秀硕士论文学位论文全文数据库 工程科技I辑》;20061024(第10期);B014-58 * |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161008 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |